This paper presents the concept of an alkali-O₂ oxidation process for producing lignin dispersants in a feasible manner at a kraft pulp mill. The oxidation process uses O₂ gas to increase the anionic charge of lignin and the final oxidised lignin can serve as a concrete plasticiser or versatile dispersant. The integrated process provides several benefits for lignin recovery, the following lignin oxidation, and recycling of chemicals. Firstly, CO₂ precipitated kraft lignin can be used without a sulphuric acid washing step. This simplifies the lignin recovery and no excess sulphur is introduced into mill cycle. As the unwashed lignin is alkaline in nature, the need for fresh alkali in the lignin oxidation is reduced. Moreover, oxidised white liquor, readily available in the mill, can be applied as a partial source of alkali. Finally, membrane filtration of the oxidised lignin solution enables the recirculation of sodium and sulphur back to the chemical cycle and provides a concentrated lignin product. Based on a simulation study, this novel concept significantly decreased the need for purging fly ash at the mill when compared to conventional lignin recovery. It was also demonstrated that the novel lignin dispersants can compete with the tested commercial oil-based plasticisers.

Three laccases, functioning in mild acidic, and one in slightly alkaline conditions, were evaluated in order to reduce low-molecular phenolic VOCs of kraft lignins, which could be used in lignin/natural fibers composites. The potential of a sulfhydryl oxidase to catalyze the oxidation of sulfur containing VOCs (thiols) was also tested in combination with the laccase-catalyzed oxidation. In addition, oxidation at alkaline pH at room temperature that may induce polymerization of phenolics in an analogous manner to the laccase-catalyzed reaction was investigated. Enzyme reactivity towards lignin was evaluated as consumption of oxygen in the reaction solution. The effect of treatments on VOC reduction was determined both by sensing (odorimetry) and chemical (TD-GC/MS, SEC) analyses. Laccases, Lcc2, and MaL from Thielavia arenaria and Melanocarpus albomyces, respectively, showed potential in reducing odors. The most promising results were obtained by oxidizing lignin with O2 at alkaline pH. However, the odor threshold values of the main VOC compounds are extremely low, which poses a challenge to VOC reduction.

Experiences of Kraft Lignin Functionalization by Enzymatic and Chemical Oxidation

Bio-based products can help us to reach sustainability goals and reduce our dependency on fossil-based raw materials. Lignin is an abundantly available bio-based material. Recently, a concept of an alkali–O₂ oxidation (LigniOx) process for feasibly producing lignin dispersants at a kraft pulp mill has been introduced. The oxidation process uses O₂ gas to increase the anionic charge of lignin and the final oxidized lignin can serve as a concrete plasticizer or versatile dispersant. Life cycle assessment (LCA) is a tool widely used to holistically evaluate the environmental benefits of various products. The goal of this study was to evaluate the versatility of the novel lignin dispersants produced from kraft lignin and to compare the environmental performance with the synthetic products using an attributional cradle-to-gate LCA. Results showed that LigniOx impacts were lower than synthetic equivalents for both the end uses—superplasticizer and dispersants—in most of the impact categories. The only negative impact was on eutrophication that arises from fly ash purging at the kraft pulping process even without the integrated LigniOx production. In addition, the production of LigniOx lignin appeared to be more attractive than conventionally recovered kraft-lignin. LigniOx contributed minimally to the total impacts with the majority of impacts arising from the kraft pulping process.

The conventional approach to converting kraft lignin (KL) into hard carbons is to start with highly purified, low-ash KL feedstocks and then rely on slow, energy-intensive oxidative stabilization and added crosslinkers to keep melting and foaming associated thermal challenges under control. Herein, we deliberately invert this paradigm. Instead of starting with highly purified KL, we retain pulping inorganics and use them as catalytic centers for oxidative crosslinking and melt suppression of KL. Spherical KL microparticles (KL-MP) were recovered from softwood black liquor by membrane filtration and spray-drying steps, intentionally retaining inorganic sodium (Na) salts as well as organically bound Na in KL-MP, and were compared to acid-precipitated, low-ash reference KL (KL-REF). During thermo-oxidative pretreatment (250 °C, 5 °C/min) in air, KL-MP undergoes inorganic-catalyzed rapid oxidative crosslinking that converts thermoplastic lignin into a rigid network, whereas KL-REF softens, foams, and fuses. Experimental analysis identifies organically bound Na-phenoxide type species as key catalytic sites. Proton magnetic resonance thermal analysis and molecular dynamics simulations reveal strongly reduced segmental mobility and Na-driven ionic clusters acting as physical crosslinking points. After pretreatment, inorganics are removed by a washing step, and the crosslinked KL-MP is carbonized, yielding low-surface-area hard carbons that retain their initial micron size and spherical morphology. As Li-ion battery anodes, the derived hard carbon shows better electrochemical performance than carbons derived from KL-REF. Overall, the work shows how otherwise undesirable inorganic impurities can simplify thermal conversion of KL, with potential for diverse applications where particle size and shape are critical.